Manufacture of nu-sulphato-alkyl compounds



. Dylan Patented Feb. 12, 1924.

UNITED STATES PATENT OFFICE.

ARTHUR GEORGE GREEN AND KENNETH HERBERT SAUNDERS. OF MANCHESTER, ENG- LAND, ASSIGNORS TO BRITISH DYESTUFFS CORPORATION LIMITED, OF MANCHES- TEE, ENGLAND.

MANUFACTURE OF N-SULPHATO-ALKYL COMPOUNDS.

No Drawing.

To all whom it may concern:

Be it known that ARTHUR GEORGE GREEN and KENNETH HERBERT SAUNDERS, subjects of the King of Great Britain and Ireland, residing at Crumpsall Vale Chemical WVorks, Blackley, Manchester, England, have invented new and useful Improvements in the Manufacture of N-Sulphato-Alkyl Compounds, of which the following is a specification.

This invention relates to the manufacture of a new class of chemical substances, namely, N-sulphato-alkyl compounds. These bodies are characterised by the presence in their structure of an alkyl sulphuric acid group attached to nitrogen, for instance, N (LIL-SUQH and upon boiling with caustic alkalies the SO H group is split off as an alkaline sulphate and the corresponding oXy-alkyl compound is produced.

It is well known that for normal dyeing, colouring matters have to be applied in the dye-bath in some-soluble form. The most usual and generally employed method of converting insoluble or insufliciently soluble colouring matters into soluble dyestuffs has been by sulphonation, that is to say, by the introduction of one or more sulphonic acid groups (SO H) into the hydrocarbon nucleus. This method was first applied to the vegetable colouring matter indigo, this insoluble colouring matter being thus converted into a soluble dye (indigo carmine) which dyes animal fibres from an acid bath. Later the basic coal-tar colouring-matters, spirit blue and magenta were converted by sulphonation into the acid colouring-matters soluble blue and acid magenta.

Insoluble azo dyes were also converted into soluble acid colouring matters by sulphonation, and it was then recognised that in the manufacture of azo dyes and of dyes of other classes the snlplionic acid group could be introduced into the components or intermediate products instead of into the finished colouring-matter.

We have now discovered a new class of dyestuffs which dye wool and silk from an acid bath, and which owe their solubility and acid character to the presence in their Application filed November 29, 1921. Serial No. 518,569.

structure of the alcoholic sulphuric acid group C H SOJ-I attached to nitrogen. This SO H group We term the fSulphato group, both in the free state and in the form of its salts. I

The introduction of the sulphato group into the structure of colour ng matters can be effected in even more varied ways than those which we have mentioned above as being in ordinary use for the introduction of the sulphonic group.

Thus the sulphato group can be introduced not only into the finished colouring matter or into a component used forthe production of the same, or into both, but there is a third alternative. The oxyethyl-residue (C H,OH) can be introduced by means of ethylene chlorhydrin into an intermediate product and this converted into a colouring matter containing this group, and then the sulphato group formed as hereinafter described.

We have thus discovered a new principle, by the use of which soluble acid colouring matters-the sulphato colouring matterscan be obtained, and in carrying out this in vention we produce a new series of intermediates, and a new series of colouring matin which R indicates an aromatic residue (or substituted aromatic residue) and A stands for a hydrogen atom, alkyl, oxyalkyl, aralkyl, or aryl group. The above formula 'arefor mono-amino derivatives, but the sulphato group can be introduced twice or more times into a colouring matter or intermediate compound, such as an orthometa-, or paramatters and intermediate diamine, in these latter cases giving intermediate sulphato acids of the types The new sulphato compounds are obtained by the action of concentrated sulphuric acid upon oxyethyl derivz-itives of aromatic amines and diamines, for instance upon bodies of 'the following types, but the invention is not confined to these 1nstances:--

Oxyethylaniline,

Dioxy-diethylanilines,

can. momma),

Oxyethyl-ethyl (or methyl) aniline,

cmamcmocmaon ciaamouaxcznton Oxyethyl-o-toluidine,

C7H7.NH(C:H4.0 H)

Oxyethyl-benzylaniline.

Oxyethylated alphaor beta-naphthylamine.

Oxyethylated ortl1o-, metaand paradiamines.

Oxyethylated amirfdphenols and aminonaphthols.

These oxyethyl derivatives (some of which are known, having been described in the German Patent No. 163043, whilst others are new) are obtained by the reaction in aqueous or alcoholic solution of ethylene chlorhydrin upon primary or secondary amines or diamines of the aromatic or fatty aromatic series, or their derivatives.

For the preparation of sulphato acids it is only necessary to treat the above or similar oxyethyl derivatives with concentrated sulphuric acid or such stronger acid as under the conditions employed will give a con1- pound completely soluble in aqueous alkalies. The conditions employed are such as would normally convert ethyl-alcohol into hydrogen ethyl-sulphate. The sulphuric acid may be replaced by fuming sulphuric acid, chlorsulphonic acid, or other agent known to be the equivalent of sulphuric acid in converting alcohols into alkyl hydrogen sulphates.

The introduction of the sulphato group into the finished dyestuff is effected by first ing such oxyethylated colours with concentrated sulphuric acid.

The preparation of the parent basic dyestufis from such oxyethyl components is effected in a manner quite analogous to that of the correspondin dyestufis from ethylaniline, diethylani ine, ethyl-o-toluidine, ethyl alpha naphthylamine, ethyl betanaphthylamine, dialkyl m phenylenediamine, dialkyl-p-phenylene-diamine, etc.

The conversion of the basic dyestufis obtained therefrom into the sulphato acids is effected by treatment with such strength of sulphuric acid and under such conditions of concentration and temperature as would normally convert ethyl-alcohol into hydrogen ethyl sulphate. Sulphato acids may be obtained by both methods in all classes of colouring-matters in which colouring matters can be obtained from the corresponding ethyl derivatives. Thus, sulphato azo dyestufls can be prepared either by use of sul phato acids or their salts in the combination, or by treatment with sulphuric acid of the finished colourin matter, or by such treatment of interme iate bodies containing oxyethyl groups. In the like manner sulphato triphenylmethane dyestuffs can be obtained by condensation from formaldehyde, benzaldehyde or substituted benzaldehydes. Again, all the types of colouring matters which can be obtained from nitroso compounds by condensation with amines, phenols or amino-phenols can be prepared from nitroso sulphate acids; or an oxyethylated azine, oxazine or thiazine colour can be converted into the sulphato acid.

A still further method of producing these dyestuffs or dyestuff components consists in first preparin the chlorethyl hydrogen sulphate (G ,CLSO H) by dissolving ethylene chlorhydrin in concentrated sulphuric acid, and reacting with this substance in a neutral or alkaline solution on a dyestufl component, dyestufl intermediate or dyestufl", containing a primary or secondary amino group. In this way the sulphato-ethyl group'-C,H,.SO,Pl-is introduced in one step.

We have hereinbefore referred to the sulphato group attached to an ethyl residue, but in all cases in which the oxyethyl group is introduced into the molecule by the use of ethylene chlorhydrin, we have found that other chlorhydrins can be used in the same way. Thus, by the use of propylene chlorhydrin or of butylene chlorhydrinon cH 4 8\Cll an oxy-propyl-group or an oxybutyl group treatment with sulphuric acid the sulphator0 1 ou or the sul hato-butl rou is forrillid T he chlorhy drins of v glyce f'ol, namely K cincl Monochlorhydrin, (lILOH onion Dichlorhydrln, (lHzOH H.Cl

and

CHzCl Epichlorhydrln,

whilst heretofore the sulphonic group has.

been used for this purpose, still the use of the sulphato group does not make it impossible to introduce the sulphonic group at the same time; by which means useful sulphato compounds of sulphonated bodies can be obtained.

Again, although we have mentioned the dyeing of wool and silk from the acid bath as characteristic of the acid properties of our new colouring-matters, their use is notrestricted to animal fibres, for some of the new sulphato dyes will dye cotton from the neutral or alkaline bath whilst some are suited for use in the manufacture of lakes and pigments. Others again possess mordant dyeing properties and can be applied, for example, upon chromed wool, or {in calico-printing.

The new dyestuffs containing sulphato groups are thus produced by the following alternative methods:

1. They can be built up from one or more components containing sulphato-ethyl, sulphato-propyl, sulphato-butyl, or sulphato glycerol groups.

2. They can be built up from one or more components containing one or more oxyalkyl groups attached to nitrogen which oxyalkyl groups are converted into sulphatoalkyl groups by treatment of the finished dyestufi' with sulphuric acid.

3. The conversion of the oxyalkyl group into the sulphato group can be eifected at an intermediate stage in the preparation, for example, by treatment with sulphuric acid of a leuco compound obtained from components containing one or more oxyalkyl groups.

4. They can be built up from components containin both oxyalkyl and sulphato groups, t e former of which can also be converted into sulphato groups by treatment of the finished dyestufi or an intermegiate stage of the same with sulphuric ac1 5. They can be produced by the introduction of sulphato groups into such finished dyestuffs or their leuco products as contain primary or secondary amido groups, by rcacting these dyestufi's or their leuco bodies with ethylene chlorhydrin or on.

hydrin and subsequently with sulphuric acid, or with the product of reaction of a chlorhydrin with sulphuric acid, such as chlorethyl hydrogen sulphate.

6. In all cases in which the use of chlorhydrins is specified they may be replaced by bromh drins, although the former are to be pre erred.

The following examples will help to further illustrate the nature of the invention as indicating the way in which it can be applied in a few cases, but we wish to guard against the impression that these examples or even their immediate analogues exhaust the cases to which the invention can be applied, nor on the other hand do we wish to confine ourselves to the manner of working in the particular cases chosen as examples.

EXAMPLE I.-SuZpkat0-ethylaniline 01" phenyZamidoethyZ-sulphuric acid.

The following are two alternative methods of preparation(a) 10 parts of oxythylanir line (obtained by the method of of D. R. P. 163043) are added to 20-30 parts of concentrated sulphuric acid. The mixture becomes warm, and on cooling sets to a thick oil which after a short time is found to be completely soluble in dilute aqueous alkalies. The substance can be obtained as its sodium salt by neutralisation with milk of lime, filtration from calcium sulphate, conversion of the calcium salt into the sodium salt sodium carbonate and evaporation to crystallization. easily soluble in' water. It is usually more convenient to neutralize with soda and use the solution directly.

(6) 10 parts of ethylene chlorhydrin are are added cautiously with cooling to 20-30 parts of concentrated sulphuric acid and the mixture allowed to stand for some hours. lit is then diluted with water, carefully neutralized with sodium carbonate and boiled for some hours with 23 parts of aniline. After making just alkaline and removing the excess of aniline by steam distillatioma solution is obtained which contains the sodium salt. of the sulphato-ethylaniline, identical with the product obtained by the previously described method.

EXAMPLE II.Disulphatodiethylaniline.

cnnamczntsomn 10 parts of dioxy-diethylaniline are added It is a white solid which is to 20-30 parts of concentrated sulphuric acid. and the mixture warmed and stirred until the solid has dissolved and a test portion is completely soluble in dilute alkali. The whole is then diluted with water and neutralized with soda. The solution can be employed directly for further comlensations. EXAVPLE III.-Sulphato-ctlzyl-o-foluidinc.

c,-n,.un.c.,m.soai

This is prepared from oxyethyl-o-toluidine by exactly analogous methods to the foregoing.

ln an analogous manner, other aromatic amines or amido compounds containing an oxyalkyl group united to nitrogen. may be sulphated by treatment with sulphuric acid. hot or cold. for longer or shorter periods, according to the case with which sulphation takes place in the compound under treatment. This varies considerably and it. is frequently noticed that those compounds to which a quinonoid structure can be assigned react more. readily than those of purely benzeuoid character.

solution containing 10 parts of sulphateethyl-o-toluidiue is prepared according to Example lll above. To this is added the solution produced by dissolving 10 parts of crystallized sodium sulphanilate in water and diazotising. Coupling takes place in mineral acid-free solution. After saltingout. the dyest-utt' is obtained as an orange powder which dyes wool yellow from an acid bath.

The following are two alternative methods of preparation (a) A solution containing 23.1 parts of the sodium salt of disulphato-diethylaniline is prepared as in Example II. To this is added a solution prepared by diazotisin 10 parts of pnitraniline. Coupling takes p ace in acetic acid solution and the resulting dye is salted-out. It is obtained as a red powder which dyes wool scarlet from an acid bath. (b) 12.3 parts of dioXy-ethylaniline are dissolved in dilute acid and coupled with the diazo solution obtained from 10 parts of p-nitraniline. An insoluble red powder is obtained which is collected and dried. On treating one part of this powder with 2-3 parts of concentrated sulphuric acid until a test portion is soluble in dilute alkali, pouring into water and salting-out, a product is obtained identical with the precedin llxnirm: V IL-N01lium salt of naphtha-- lcn12ulplz(1-050-p-(lisulplmfo (licthylaminolmnzenc.

th.N .t l .N(C ll .S() Na) 12.4 parts of di-oxyethyl-aniline are sulphated as in Example II. The solution of the sodium salt is cooled and to it is added at ()-5 C. a solution obtained by diazotising parts of alpha-naphthylaminc. Free mineral acid is removed by the addition of sodium acetate and the mixture is stirred until it no longer gives a colour reaction with H-Acid. The dyestutf is then salted iit, collected and dried. The product is a dark brown powder which dyes wool orange from an acid bath. The dyestutf may also be produced, though less advantageously, by coupling di-oxyethyl-aniline with diazotised alpha-naphthyla-mine and subsequent sulphation of the product.

To an acid solution of 22.1 parts of disulphato-diethylaniline a solution of nitrite is added with cooling and stirring. A red solution of the nitroso hydrochloride is ob tained, and when all the amine has been conyerted, this is reduced in acid solution with zinc dust. After removal of excess of zinc, nitrite is again added to the clear solution and the diazo solution thus produced is coupled with 10 parts of B-naphthol. The product is a dark powder which dyes wool maroon from an acid bath.

Exam ne X.-DisuZphatodiethyldiaminoditolyl-phenyl carbinol.

10 parts ofthe dyestufi obtained/according to I). R. 1. No. 278423 by. condensing benzaldehyde with oxyethyl-o-toluidine and subsequent oxidation with lead peroxide, is added cautiously to 2030 parts of cold concentrated sulphuric acid, care being taken that the temperature does not rise unduly.

The homogeneous solution is allowed to stand until the pr0duct is soluble in cold chlute alkali. The solution is then diluted and the dyestufi' salted-out as adark powder with a copper reflex. It dyes wool a green blue from an acid bath.

EXAMPLE XI.

CzHs o nacn nmezmsoi C5HE.CH3='N.TCQH4.SQ4H They dye wool from an acid bath giving very level yellowish green, bluish green and sky blue shades respectively.

It is possible to sulphate the leuco bases in all the four preceding examples before oxidation to the carbinol, but the method of working described above is regarded as preferable.

EXAMPLE XII."[ntemaZ salt of disulphatodietiz-yb (Methyl dimethyl trianw'xno tri- 17 parts of dioxyethyl-diethyldiaminodiphenyl-methane obtained by condensing oxyethyl-ethyl-aniline hydrochloride with formaldehyde,-are heated with 100 parts of sulphuric acid, sp. gr. 1.84, at a temperature of 100 C. until a test no longer gives a precipitate with alkali. The time required is about 4 hours. The solution is cooled, poured into 1,000 parts of water and lime or chalk added until neutrality to Congo paper is reached. The calcium sulphate is filtered 01? and extracted with hot water. The filtrate and washings having been brought to 35 (1., 3 parts of dimethyl aniline are added with continuous stirring. After 15 minutesa strong solution of 6 parts of'potassium bichromate is run in and the whole stirred at 35-40 C. for 24 hours. The liquid is filtered from the chromium oxide and the dyestuff thrown out with salt, filtered and dried at 100 C. It is obtained as a copper coloured powder and dyes wool in extremely level violet shades from an acid bath.

Dyes of the same type differing slightly in shade from the above are obtained by the use of 3.2 parts of ethyl-o-toluidine or 3.4 parts of diethyl-aniline in the above example.

EXAMPLE XIII.l'nternaZ salt of disulphato-dz'ethyZ-tetmmethyl trz'amino-triphenyl carb'inol. I

13.5 parts of tetramethyl-diamino-diphenyl carbinol (Michlers hydrol) are heated with filtered oil, washed and dried.

21.65 parts of the dry leuco compound are heated to 100 C. with 110 parts of sulphuric acid 1.84 sp. gr. until a test portion gives a clear solution in alkali. The solution is poured into 1000 parts of water and lime or chalk added until the acid reaction to Congo paper has disappeared. The calcium sulphate is removed and well washed with hot water. The filtrate is cooled to below 5 (3., strongly stirred while there are added to it 40 parts of 30% lead peroxide paste, followed by parts of 10% hydrochloric acid. Stirring is continued for two hours. The sparingly soluble dyestutf is then collected, dried at 100 0., and ground. It forms a copper coloured powder and dyes wool a clear purple from an acid bath.

EXAMPLE X1V.Dz'salphato diethg Z dzethy l da/mino omy tm'phmyl carbinol carbowg late.

10.5 parts of diethyl-dioxyethyl-diarnidodiphenyl methane omega sulphonic acid are heated with .parts of sulphuric acid monohydrate to 100 C. for 2 hours;

parts of salicylic acid are then added and the mixture heated for a further 3 hours. It is then poured into 400 parts of water and lime or chalk added until the liquid is no longer acid to Congo red paper. The calcium sulphate formed is filtered off and extracted. The filtrate is cooled to below 10 C. and 20 parts of a 30% lead peroxide paste added, followed by 27 parts of a 10% solution of hydrochloric acid, the whole being stirred for two houis. The liquid is then heated to C., 4 parts of sodium sulphate added, the lead is filtered off as sulphate, and the dye precipitated by the addition of salt."

The product is obtained as a violet powder which dyes Wool by the after-chrome method a bright reddish-violet shade, and is valuable in calico printing with chrome mordant thickenin By sulistituting o-cresotinic acid for salicylic acid in this example, abright violet dyestufi' of similar properties is obtained. By substituting benzoic acid, o-toluic acid, naphthalene sulphonic acid, or R-salt, acid dyestuffs of green shade are produced.

The omega sulphonic acid employed for these condensations is prepared as follows 165 parts of oxethyl-ethyl-aniline is agitated for 3 days at 100 C. with 43.2 parts of formaldehyde (40% solution by volume) and 140 parts of water containing 2 parts of sulphuric acid. After cooling the methane base is filtered ofi and dried. 3 12 parts of the mathane base are dissolved in 345 parts of 80% formic acid, diluted with 1200 parts of water, cooled to 0 C. and oxidized by addition of lead peroxide paste containing 263 parts PbO After 45 minutes stirring, 220 parts sodium sulphate are added and the'solution is filtered from lead sulphate. The filtrate is made alkaline, and the precipitated hydrol is filtered ofi. The latter is redissolved in 345 parts of 80% formic acid and as little water as possible, andto it is added 80 parts of sodium bisulphite solution (38%39%). The mixture is heated to 6065 C. for 4 hours, allowed to cool and made faintly alkaline with caustic soda. After filtration from any tarry residue the solution is fil-' The sodium tered and saturated with salt. salt of the omega sulphonic acid separates on standing. From this the free acid is obtained by redissolving in 1300 c. c. of

twice normal hydroloric acid and neutralizing until only a faint acidity to litmus remains, when on standing the product separates.

In the condensations in which a diphenylmethane-omega-sulphonic acid is used,-this may be replaced by the corresponding carbinol (hydrol) of which it is the bisulphite compound.

EXAMPLE XV.-Intem-aZ .sa Zt of disulphato d'z'ethyZ-dimethyZ-dimnino phenazonium.

A basic azine dyestuff is prepared by the action of nitroso-dimethylaniline on symdioxyethyl-m-phenylene-diamine, as for example by the method described in Example .IX of British patent specification No. 22991 of the 30th August 1921. The product so obtained is treated with cold sulphuric acid, sp. gr. 1.84, under the conditions described in Example X above. The resulting acid dyestulf is a black powder, very soluble in water and dyeing an acid bath.

EXAMPLE XVI.SuZphato-ethylamin0-diomy-toluphenomazonium carbomg/lz'c acid.

. N cimsoma .Nacuiacrn cunomaoo1 A dyestufi of the gallocyamide type is prepared by the usual method from pnitroso-oxyethyl-o-toluidine and gallic acid (see Examples I and II of British patent specification No. 22991 of the 30th August 1921). 10 parts of the dried product are added to 20-30 parts of concentrated sulphuric acid which is gently warmed until a sample gives no precipitate with tannin reagent. After dilution and salting out, the dyestuff is obtained as a black powder which dyes WOOl a deep blue from an acid bath, and a violet blue upon wool mordanted with chromium oxide.

EXAMPLE XVII-Jnlfernal salt of disulphat0-diethyl-benzyZ-diamino-naphth0- phenowazz'ne.

A basic dyestuff is prepared by the condensation of nitroso-dioxyethyl-m-aminohenol with benzyl-alpha-napthylamine, as or example by the method described in Example V of British patent specification No. 22991 of the 30th August 1921. 10 parts of this compound are dissolved in 20-30 parts of cold sulphuric acid, sp. gr. 1.84, and allowed to stand until a test dissolves to a clear red solution in alkali. It is then poured into brine and ice, the precipitated dye filtered off and the filter cake dissolved with stirring in 10% caustic soda. The soluwool a fast reddish-blue from tion is filtered to remove traces of unsulphated base and poured into a slight excess of hydrochloric acid. The complete preclpltation of the dye is brought about by a little salt. The dye is collected and dried, yielding a bronzy powder, readily soluble in hot water and dyeing wool a pure blue from an acid bath. 7

EXAMPLE XVIII.InternaZ salt of disulphato-diethyZ-cliamid?)-dit0lathiazine.

EXAMPLE XIX.Oxaz'ine dyestufl of the constitution.

noiscin/ I By the condensation of nitroso-oxyethylethylaniline with gallanilide a basic galloc anine is obtained, which is further conensed with asym-dioxyethyl-p-phenylene diamine yielding a sparingly soluble procluct (see Examples II and III of British patent specification No. 22991 of the 30th August 1921). then treated with 2030 parts of concentrated sulphuric acid, warming if necessary to complete solution. Care must be exercised to prevent the acid from attacking the nucleal hydroxy groups or the mordant dyeing properties of the sulphato dye are impaired. When a test sample is completely soluble in water or dilute acid, the sulphuric acid solution is diluted, neutralized with caustic soda and the sodium salt thrown out with common salt. It should dissolve to a deep blue solution in water and give no precipitate on acidifying. It dyes wool a pure blue from an acid bath and can be chromed to give rather a greener shade. It can be applied for printing purposes.

A solution of 10 parts of disulphato-di- 'ethylaniline is added to the tetrazo solution SO4H 10 parts of dioxypropylaniline, obtained 10 parts of this product are by boiling aniline in excess with an aqueous solution of glycerine chlorhydrin, are dissolved in dilute acid and coupled with the diazo solution obtained from 12 parts of p-nitraniline. The coupling product is collected and dried. It is then sulphated in the manner, indicated in Example VI B, and

yields a dye of almost identical properties.

EXAMPLE XXIL-(Salphation by means of chlorosalphonic acid.)

EXAMPLE XXIII.S0dimn. salt of benzeneazo-dzsalpkato-pa'opylamido benzene.

CgH5-N-N-C5H4.NH.CH:.CH(SO H).CH:(SO4H) 10 parts of dioxypropylaniline, obtained as above described, are treated with 14: parts of chlorsulphonic acid as in the previous example. The semi-solid mass produced is dimolved in water, neutralized with sodium carbonate, and coupled with a, solution of diazobenzene chloride obtained from 4.6 parts of aniline. The dyestufi' is salted-out and separated. It dyes wool yellow from an acid bath.

What we claim is 1. As new products the i -sulphato-alkyl compounds which contain at least one alkyl sulphuric acid group attached to nitrogen and on boiling with caustic alkalies split off the SOJ-I groups as alkaline sulphate.

2. As new products the N-sulphato-ethyl compounds which contain at least one ethyl sulphuric acid group attached to nitrogen N-(l l LOSO H and on boiling with caustic alkalies split ofi' the'SO H groups as alkaline sulphate. j

3. As new compounds acid dyestuffs which are N -sulphato-alkyl compounds containing at least one alkyl sulphuric acid group which upon boiling with caustic alkali split off the SO H groups as alkaline sulphate.

4. As new compounds acid dyestufi's which are l\'-sulphato-ethyl compounds containing at least one ethyl sulphuric acid group which upon boiling with caustic alkali split off the SO H groups as alkaline sulphate.

5. As new compounds acid triarylmethane colouring matters which are N -sulphato alkyl compounds containing at least one alkyl sulphuric acid group attached to nitrogen and which upon treatment with caustic alkalies split off the SO H groups as alkaline sulphate.

6. As new compounds acid triarylmethane colouring matters which are N-sulphato-ethyl compounds containing atleast one ethyl sulphuric acid group attached to nitrogen and which upon treatment with caustic alkaliessplit off the SO H groups as alkaline sulphate.

7. As new compounds acid triphenylmethane colouring matters which are N-sulphato-alkyl compounds containing at least one alkyl sulphuric acid group attached to nitrogen and which upon treatment with caustic alkalies split off the 80 R groups as alkaline sulphate.

8. As new compounds acid tripl1cnly1nethane colouring matters which are "N-sulphato-ethyl compounds containing at least one ethyl sulphuric acid group attached to nitrogen and which upon treatment. with caustic alkalies split off the SOJ'I groups as alkaline sulphate.

9. As new compounds acid mordant dyeing triarylmethane colouring matters contalning a carboxy group which are N -sulphato-alkyl compounds containing at least one alkyl sulphuric acid group attached to nitrogen and which upontreatment with caustic alkalies split off the SO H groups as alkaline sulphate.

10. As new compounds acid mordant dyeing triarylmethane colouring matters containing a carboxy group which are N-sulphato-ethyl compounds containing at least one ethyl sulphuric acid group attached to nitrogen and which upon treatment with caustic alkalies split ofl the SO H groups as alkaline sulphate.

11. As new compounds green acid mordant dyeing triphenylmethane colouri'n matters which contain acarboxy group and are N-sulphato-ethyl compounds containing at least one ethyl sulphuric acid group attached to nitrogen and which upon treatment with caustic alkalies split off the SO H groups as alkaline sulphate.

In testimony whereof we have signed our names to this specification.

ARTHUR GEORGE GREEN. KENNETH HERBERT SAUNDERS. 

